Sample introduction system with mixing

ABSTRACT

A sample introduction system provides mixing of a sample and a diluent within the container via gas injection. In one or more implementations, the sample introduction system causes a probe of an autosampler to be inserted into a container containing a sample and a diluent so that an end of the probe is submerged beneath a surface of the diluent and the sample. Gas is then injected through the probe to mix the sample and the diluent within the container. An aliquot of the mixed sample and diluent is then withdrawn through the probe.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation under 35 U.S.C. §120 of U.S.patent application Ser. No. 13/868,300, filed Apr. 23, 2013, and titled“SAMPLE INTRODUCTION SYSTEM WITH MIXING,” and U.S. patent applicationSer. No. 12/881,906, filed Sep. 14, 2010, and titled “SAMPLEINTRODUCTION SYSTEM WITH MIXING,” which itself claims priority under 35U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/242,217,filed Sep. 14, 2009, and titled “SAMPLE INTRODUCTION SYSTEM WITHMIXING.” U.S. patent application Ser. Nos. 13/868,300 and 12/881,906 andU.S. Provisional Application Ser. No. 61/242,217 are herein incorporatedby reference in their entireties.

BACKGROUND

Inductively coupled plasma (ICP) mass spectroscopy is an analysistechnique commonly used for the determination of trace elementconcentrations and isotope ratios in liquid samples. ICP massspectroscopy employs electromagnetically generated partially ionizedargon plasma which reaches a temperature of approximately 7000K. When asample is introduced to the plasma, the high temperature causes sampleatoms to become ionized or emit light. Since each chemical elementproduces a characteristic mass or emission spectrum, measuring saidspectra allows the determination of the elemental composition of theoriginal sample.

Sample introduction systems may be employed to introduce the liquidsamples into the ICP mass spectroscopy instrumentation (e.g., aninductively coupled plasma mass spectrometer (ICP/ICPMS), an inductivelycoupled plasma atomic emission spectrometer (ICP-AES), or the like) foranalysis. For example, a sample introduction system may withdraw analiquot of a liquid sample from a container and thereafter transport thealiquot to a nebulizer that converts the aliquot into a polydisperseaerosol suitable for ionization in plasma by the ICP mass spectrometryinstrumentation. The aerosol is then sorted in a spray chamber to removethe larger aerosol particles. Upon leaving the spray chamber, theaerosol is introduced to the ICPMS or ICPAES instruments for analysis.Often, the sample introduction is automated to allow a large number ofsamples to be introduced into the ICP mass spectroscopy instrumentationin an efficient manner.

SUMMARY

A sample introduction system is described that provides mixing of asample and a diluent within the container via gas injection. In one ormore implementations, the sample introduction system causes a probe,such as the probe of an autosampler, to be inserted into a containercontaining a sample and a diluent so that an end of the probe issubmerged beneath a surface of the diluent and the sample. Gas is theninjected through the probe to mix the sample and the diluent within thecontainer. An aliquot of the mixed sample and diluent is then withdrawnthrough the probe.

This Summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This Summary is not intended to identify key features oressential features of the claimed subject matter, nor is it intended tobe used as an aid in determining the scope of the claimed subjectmatter.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description is described with reference to the accompanyingfigures. In the figures, the left-most digit(s) of a reference numberidentifies the figure in which the reference number first appears. Theuse of the same reference numbers in different instances in thedescription and the figures may indicate similar or identical items.

FIGS. 1A, 1B, and 1C are illustrations of an environment in an exampleimplementation that employs a sample introduction system that providesmixing using gas injection.

FIG. 2 is a flow diagram illustrating a procedure that may be employedby a sample introduction system such as the sample introduction systemof the environment shown in FIGS. 1A, 1B, and 1C to mix a sample anddiluent using gas injection and withdraw an aliquot of the mixed sampleand diluent.

FIGS. 3A, 3B, 3C, and 3D are illustrations depicting an examplecontainer containing a sample and diluent during mixing of the sampleand diluent using gas injection and withdrawal of a aliquot of mixedsample and diluent in accordance with the procedure of FIG. 2.

FIGS. 4A and 4B are illustrations depicting cleaning of the screen of ascreened probe using gas injection.

FIG. 5 is a flow diagram illustrating a procedure in an exampleimplementation to add a diluent to a sample and insert the sample anddiluent into a container.

FIG. 6 is an illustration depicting the addition of a diluent to asample in accordance with the procedure of FIG. 5.

DETAILED DESCRIPTION

Overview

ICP mass spectroscopy may be used in the analysis of oil samples. Forexample, ICP mass spectroscopy analysis of motor oil is often used byenterprises that maintain a large number of vehicles. Parts that wear inan engine will deposit trace metals in the engine's oil. Analysis of theused motor oil of an engine provides information about how the engine isoperating by identifying worn parts within the engine. In addition, ICPmass spectrometry analysis can determine the amounts of the original oiladditives remain within the oil after a period of use, thus providing anindication of the amount service life the oil has remaining.

When samples of oil are analyzed, a diluent such as kerosene may beadded to reduce the viscosity of the oil allowing an aliquot of thesample to be withdrawn for analysis. Generally, the oil sample and thediluent are provided in a container in an unmixed state. Consequently,prior to taking an aliquot of the sample for ICP mass spectrometryanalysis, the sample and diluent are first mixed.

Accordingly, a sample introduction system is described that providesmixing of a sample and a diluent within the container via gas injection.The sample introduction system includes an auto sampler configured toinsert a probe into a container holding a sample and a diluent so thatan end of the probe is submerged beneath the surface of the sample andthe diluent. A valve assembly is configured to cause gas to be injectedinto the container through the probe to mix the sample and the diluentwithin the container via bubbling. For example, in one or moreimplementations, the gas is injected in a series of short bursts to mixthe sample and diluent. The valve assembly may then be configured tocause a vacuum to be applied to the probe to withdraw an aliquot of themixed sample and diluent through the probe into a sample loop. By mixingthe oil with the same probe that withdraws the aliquot through gasinjection, the throughput of the sample introduction system is increasedin comparison with sample introduction systems that use separate mixingapparatus. For example, in one implementation, the analysis time persample of the sample introduction system may be reduced to less thanabout 24 seconds. Additionally, in implementations where a screenedprobe is used, the injection of gas through the probe may cause fibrouscontaminants to be removed from the screen.

In the following discussion, an example environment is first described.Example functionality is then described that may be implemented by thesample introduction system in the exemplary environment, as well as inother environments without departing from the spirit and scope thereof.

Example Environment

FIGS. 1A, 1B, and 1C illustrate an environment 100 in an exampleimplementation that employs a sample introduction system 102 whichprovides mixing of samples with diluent using gas injection. As shown,the sample introduction system 102 includes a probe 104 that comprises ahollow tubular structure configured to be inserted into a container 106that holds a sample to which a liquid diluent has been added. In theimplementation illustrated, the probe 104 includes a single internalpassageway through which gas is injected into the sample and diluent,and through which the aliquot of the mixed sample and diluent iswithdrawn. In embodiments, the probe 104 may include an integral supportformed of a generally rigid material such as carbon fiber, stainlesssteel, polyaryletheretherketone (PEEK), polyetherimide (PEI), or thelike, encapsulated with polytetrafluoroethylene (PTFE). However, otherprobe structures are possible. Example probes 104 are shown in greaterdetail in FIGS. 3B, 3C, 3D, 4A, 4B, and 6.

The probe 104 may be coupled to an autosampler 110 that moves the probe104 among a plurality of containers 106 in a tray or rack in apredetermined order. The autosampler 110 inserts the probe 104 into eachof the containers 106 so that an aliquot of the diluted sample may bewithdrawn for analysis. After the probe 104 is withdrawn from acontainer 106, the autosampler 110 may rinse the probe 104 by insertingthe probe 104 into a rinse station 112 containing a suitable rinsefluid, such as the diluent, or the like.

The autosampler 110 may provide functionality to control operation ofother components of the sample introduction system 102. Control ofcomponents of the sample introduction system 102 may also be provided bya separate control module, a general purpose computer, or the like. Inthe implementation shown, the autosampler 110 may be configured inaccordance with one or both of U.S. Pat. Nos. 7,201,072 and 7,469,606,which are herein incorporated by reference in their entireties. However,autosamplers 110 having other configurations may be employed.

The sample introduction system 102 further includes a valve assembly 108coupled to the probe 104 via a capillary 114. The valve assembly 108 isconfigured to cause gas to be injected into a container 106 in which theprobe 104 has been inserted, through the capillary 114 and probe 104 tomix the sample and the diluent within the container 106 via bubbling.The valve assembly 108 then causes a vacuum to be applied to the probe104 via the capillary 114 to withdraw an aliquot of the mixed sample anddiluent through the probe 104 and capillary 114 into a sample loop 116,which temporarily holds the aliquot.

In the example implementation illustrated, the valve assembly 108includes a first valve 118 and a second valve 120. The first valve 118comprises a six port valve that includes a first port 122, a second port124, a third port 126, a fourth port 128, a fifth port 130, and a sixthport 132, while the second valve 120 comprises a four port valve thatincludes a first port 134, a second port 136, a third port 138, and afourth port 140.

The first valve 118 may be actuated between a first state, shown inFIGS. 1A and 1B and a second state, shown in FIG. 1C. When the firstvalve 118 is actuated to its first state, the first valve 118 connectsthe first port 122 with the sixth port 132, the second port 124 with thethird port 126, and the fourth port 128 with the fifth port 130 to allowflow between the respective pairs of connected ports. Conversely, whenthe first valve 118 is actuated to its second state, the first valve 118instead connects the first port 122 with the second port 124, the thirdport 126 with the fourth port 128, and the fifth port 130 with the sixthport 132 to allow flow between the respective pairs of connected ports.

The second valve 120 may similarly be actuated between a first state,shown in FIGS. 1A and 1C, and a second state, shown in FIG. 1B. When thesecond valve 120 is actuated to its first state, the second valve 120connects the first port 134 with the fourth port 140 and the second port136 with the third port 138 to allow flow between the respective pairsof connected ports. Conversely, when the second valve 120 is actuated toits second state, the second valve 120 instead connect the first port134 with the second port 136 and the third port 138 with the fourth port140 to allow flow between the respective pairs of connected ports.

As shown, the sample loop 116 is coupled to, and extends between, thefirst port 122 and the fourth port 128 of the first valve 118. Thesample loop 116 is comprised of a loop of tubing having a lengthsufficient to hold at least a portion of the aliquot of mixed sample anddiluent withdrawn from a container 106. In embodiments, the sample loop116 is formed of a suitable material, such as PTFE, or the like.However, it is contemplated that the sample loop 116 may have otherconfigurations. For example, the sample loop 116 may include a column,or like component, that is configured to further process (e.g., filter)the sample and diluent.

A diluent carrier is furnished via a line 142 coupled to the sixth port132 of the first valve 118. The diluent carrier may be supplied from areservoir 144 of diluent by a pump (a peristaltic pump 146 isillustrated) at a predetermined flow rate. For example, in embodimentswhere the sample introduction system 102 is used in the analysis of oilsamples, the diluent carrier may be kerosene supplied at a flow rate ofat least about 2 mL/min. However, the use of other flow rates iscontemplated.

In the example implementation shown, a nebulizer 148 is interconnectedwith the valve assembly 108 via a line 150 coupled to the fifth port 130of the first valve 118. As noted, the nebulizer 148 converts mixedsample and diluent received from the sample loop 116 into a polydisperseaerosol suitable for ionization in plasma by the ICP mass spectroscopyinstrumentation 152 (e.g., ICPMS, ICPAES, or the like). The aerosol isthen sorted in a spray chamber 154 to remove larger aerosol particles.Upon leaving the spray chamber 154, the aerosol is introduced to the ICPmass spectroscopy instrumentation 152 for analysis.

The capillary 114 of the probe 104 is coupled to the third port 126 ofthe first valve 118. In embodiments, the capillary 114 comprises alength of tubing formed of a suitable material, such as PTFE, or thelike, which is sufficiently flexible to allow movement of the probe 104by the autosampler 110.

A second port 124 of the first valve 118 is coupled to the first port134 of the second valve 120 via line 156. A supply of gas is furnishedvia a line 158 coupled to the fourth port 140 of the second valve 120.The gas supplied via line 158 may be any gas suitable for use with thesample and diluent. For example, in embodiments where the sampleintroduction system 102 is used in the analysis of oil samples, the gassupplied may be Argon (Ar) or Nitrogen (N₂). As shown, the gas may besupplied from a source 160 such as a pressurized tank, or the like. Aregulator 162 regulates the pressure of the gas. For example, inembodiments where the sample introduction system 102 is used in theanalysis of oil samples, the pressure may be regulated to about 0.25 barby the regulator 162. However, regulation of the pressure of the gassupplied to line 158 to other pressures is contemplated.

A vent line 164 may be connected to the third port 138 of the secondvalve 120. In some embodiments, the vent line 164 may vent unused gas toatmosphere. In other embodiments, the vent line 164 may be coupled to agas collection system to collect unused gas, for example, to berecycled. In further embodiments, vent line 164 may be capped so thatunused gas does not vent.

A vacuum is supplied to the second port 136 of the second valve 120 vialine 166. In embodiments, the vacuum may be supplied by a vacuum pump168 coupled to line 166. In the implementation shown, the vacuum pump168 is configured as a component of the autosampler 110. However, it iscontemplated that the vacuum pump 168 may also be a separate componentof the sample introduction system 102, may be combined with anothercomponent of the sample introduction system 102 such as a controlmodule, or the like.

A first waste line 170 may be coupled to the vacuum pump 168 (e.g., theautosampler 110). Similarly, a second waste line 172 may be coupled tothe spray chamber 154. The waste lines 170, 172 receive excess sampleand/or diluent from the autosampler 110 and/or the spray chamber 154,respectively. In embodiments, a waste receptacle 176 may be coupled tothe waste lines 170, 172 to receive the excess sample and/or diluent fordisposal. A pump (a peristaltic pump 174 is shown) may be provided todraw the excess sample/diluent through the second waste line 172 fromthe spray chamber 154.

In embodiments, lines 142, 150, 156, 158, 164, 166, 170, 172 maycomprise lengths of flexible tubing formed of a suitable material, suchas PTFE, or the like. However, other configurations are possible.

FIGS. 1A, 1B, and 1C illustrate an example implementation of the sampleintroduction system 102 which provides mixing of samples with diluentusing gas injection. However, it is contemplated that otherimplementations are possible. For example, a sample introduction system102 in another implementation may employ a valve assembly that utilizesa single multiple-port valve, a valve assembly that utilizes three ormore valves, and so on. Similarly, a sample introduction system 102 inanother implementation may employ a separate control module in additionto the autosampler 110.

Example Procedures

FIG. 2 illustrates an example procedure 200 suitable for use by thesample introduction system 102 in the environment 100 of FIGS. 1A, 1B,and 1C to mix a sample and diluent within a container 106 using gasinjection and withdraw an aliquot of the mixed sample and diluent foranalysis. As shown in FIG. 2, one or more containers that contain asample and a diluent in an unmixed state are received for analysis(Block 202). For instance, as shown in FIGS. 1A, 1B, and 1C, containers106 containing various samples to which a diluent has been added may bereceived in a sample tray of the autosampler 110 in preparation foranalysis of the samples by the ICP mass spectroscopy instrumentation152.

FIGS. 3A, 3B, 3C and 3D illustrate an example container 106, in thisinstance a sample vial 300, that contains a sample 302 and diluent 304.FIG. 3A shows the sample vial 300 while the sample 302 and diluent 304are in an unmixed state. Because the sample 302 is normally denser thanthe diluent 304, the sample 302 may tend to settle to the bottom surface308 of the sample vial 300, while the diluent 304 tends to float on topof the sample 302. For example, in embodiments where the sampleintroduction system 102 is used in the analysis of oil samples, thesample 302 may comprise used engine oil, while the diluent 304 iscomprised of kerosene which, being less dense tends to float on thesurface of the oil. In one or more such embodiments in which the oil isdiluted by a factor of ten (e.g., a 10× dilution), the sample vial 300may be sized to contain approximately 1 ml of oil diluted with 9 ml ofkerosene.

Referring again to FIG. 2, the probe 104 is then inserted into a firstof the containers 106 (Block 204). In embodiments, the sampleintroduction system 102 may cause the autosampler 110 to insert theprobe 104 into the container 106 until the end of the probe 104 is in aposition proximal to a bottom surface of the container 106.

FIG. 3B illustrates the sample vial 300 containing a sample 302 anddiluent 304 shown in FIG. 3A, in which a probe 104 has been inserted. Asshown, the probe 104 is inserted into the sample vial 300 until the end306 of the probe 104 is in a position proximal to the bottom surface 308of the container 106. Thus, the end 306 of the probe 104 is generallysubmerged within the sample 302.

The sample and diluent are next mixed (Block 206) by injecting gas intothe container 106 through the probe 104 to cause bubbling of the sampleand diluent. For example, as shown in FIG. 1A, the first valve 118 isactuated to its first state so that the second port 124 of the firstvalve 118 is connected with the third port 126 to couple the capillary114 to line 156. The second valve 120 is also actuated to its firststate so that the first port 134 of the second valve 120 is connectedwith the fourth port 140 to couple line 156 with line 158. In thismanner, gas is supplied to the probe 104 from the gas source 160 forinjection into the container 106.

FIG. 3C illustrates injection of a gas 310 into the sample vial 300 bythe probe 104 to mix the sample 302 and diluent 304 via bubbling. In oneor more embodiments, gas may be injected in a series of short bursts tomix the sample 302 and diluent 304. Use of short burst of gas providesefficient mixing of the sample 302 and diluent 304, while preventing thesample 302 and diluent 304 from bubbling over the top 312 of the samplevial 300. It is contemplated the length of each burst and/or the periodseparating successive bursts may be constant or may vary (e.g., increaseor decrease, be randomly selected, and so on). Thus, the number andlength of the bursts, and the period separating the bursts may beselected to maximize the efficiency of mixing of the sample 302 anddiluent 304. For instance, in embodiments where the sample introductionsystem 102 is used in the analysis of oil samples, gas 310 may beinjected in three or more bursts having durations of about 0.1 secondseach, separated by periods between successive bursts of about 0.1seconds in duration.

The probe 104 may then be retracted (Block 208) by the autosampler 110.For example, as shown in FIG. 3D, the probe 104 may be withdrawn fromthe position shown in FIG. 3C, wherein the end 306 of the probe 104 isproximal to the bottom surface 308 of the sample vial 300 followinginjection of the gas 310 and mixing of the sample 302 and diluent 304.The probe 104 may be withdrawn until the end 306 of the probe 104 isspaced away from the bottom surface 308 but is held beneath the surface314 of the mixed sample and diluent 316.

An aliquot of the mixed sample and diluent is then withdrawn from thecontainer 106 (Block 210). For example, as shown in FIG. 1B, afterinjection of the gas, the first valve 118 is actuated to its secondstate so that the first port 122 of the first valve 118 is connectedwith the second port 124 and the third port 126 is connected with thefourth port 128 to couple the sample loop 116 between the capillary 114and line 156. The second valve 120 is also actuated to its second stateso that the first port 134 of the second valve 120 is connected with thesecond port 136 to couple line 156 with line 166. In this manner, avacuum is applied to the probe 104 to draw the mixed sample and diluentthrough the probe 104 and capillary 114 into the sample loop 116. FIG.3D illustrates the position of the probe 104 within the sample vial 300during withdrawal of the aliquot of the mixed sample and diluent 316.

While the first and second valves 118, 120 are actuated to their secondstates as shown in FIG. 1B, the fifth port 130 of the first valve 118 iscoupled to the sixth port 132 to couple line 142 to line 150 so thatcarrier diluent may be supplied to the nebulizer 148 to rinse theinjector of the nebulizer 148. Moreover, the third port 138 of thesecond valve 120 is connected to the fourth port 140 so that excessmixed sample and diluent 316 may be ported to the waste receptacle 176via vent line 164.

Referring again to FIG. 2, the probe 104 is then removed from thecontainer 106 (Block 212) by the autosampler 110 and rinsed (Block 214).In the implementation illustrated in FIGS. 1A, 1B, and 1C, theautosampler 110 may cause the probe 104 to be moved to and insertedwithin the rinse station 112. A rinse fluid (e.g., the diluent) may thenbe drawn through the probe 104. Simultaneously, the aliquot of mixedsample and diluent that was drawn into the sample loop 116 may beprovided to the nebulizer 148 for conversion into a polydisperse aerosolsuitable for ionization in plasma by the ICP mass spectroscopyinstrumentation 152.

As shown in FIG. 1C, the first valve 118 is actuated to its first stateso that the second port 124 of the first valve 118 is connected with thethird port 126 to couple the capillary 114 to line 156. The second valve120 is actuated to its second state so that the first port 134 of thesecond valve 120 is connected with the second port 136 to couple line156 with line 166. In this manner, a vacuum is applied to the capillary114 to draw rinse fluid through the probe 104, the capillary 114, firstvalve 118, line 156, second valve 120, and line 166. The rinse fluid isthen transported to the waste receptacle 176 via waste line 170.

The first port 122 of the first valve 118 is also connected with thesixth port 132, while the fourth port 128 of the first valve 118 isconnected with the fifth port 13 to couple line 142 to line 150. In thismanner, diluent carrier supplied from the reservoir 144 of diluent byperistaltic pump 146 may be used to advance the aliquot of mixed sampleand diluent that was drawn into the sample loop 116 into the nebulizer148.

If additional samples are to be analyzed (“Yes” from Decision Block216), the probe 104 is inserted into the next container 106 containing asample to be analyzed, and the procedure 200 (Blocks 204-216) isrepeated. When no more samples remain to be analyzed (“No” from DecisionBlock 216), the procedure 200 may be halted or paused until additionalcontainers 106 are received for analysis (Block 202).

It is contemplated that, in one or more embodiments, the probe 104 maybe rinsed (Block 214) prior to initial insertion of the probe 104 intothe first of the containers 106 (Block 204) as described above. Further,gas may be injected through the probe 104 while the probe 104 is rinsed(Block 214). For example, in some embodiments, the probe 104 may employa screen member (e.g., a screen, a filter, or the like) to filterfibrous contaminants from the sample and diluent so that thecontaminants do not enter the probe 104. The injection of gas throughthe probe 104 may have the effect of causing the fibrous contaminants tobe removed from the screen during rinsing and/or during mixing of thesample and diluent.

Injection of gas by the sample introduction system 102 may beaccomplished by actuating the first and second valves 118, 120 to theirfirst state while the probe 104 is inserted within the rinse station 112by the autosampler 110. As shown in FIG. 1A, the second port 124 of thefirst valve 118 is thus connected with the third port 126 to couple thecapillary 114 to line 156, while the first port 134 of the second valve120 is connected with the fourth port 140 to couple line 156 with line158, so that gas is supplied to the probe 104 from the gas source 160.The second valve 120 may be actuated to its first state either before orafter injection of the gas to draw the rinse solution through the probe104 as described above.

FIGS. 4A and 4B illustrate an example probe 104, in this instance ascreened probe 400, that is cleaned using gas injection in accordancewith the present disclosure. As shown, the probe 400 comprises a hollowtubular structure 402 having an end that includes a screen member 406.As shown in FIG. 4A, fibrous contaminants 408 filtered by the screenmember 406 may tend to collect on the screen member 406, possiblyreducing the flow of sample and diluent into the probe 400. As shown inFIG. 4B, the injection of gas through the probe 400 may dislodge atleast some of the fibrous contaminants 408 from the screen member 406into the rinse fluid during rinsing and/or into the sample and diluentduring mixing.

FIG. 5 illustrates a procedure 500 in an example implementation that issuitable for use by the sample introduction system 102 in theenvironment 100 of FIGS. 1A, 1B, and 1C to add a diluent to a sample. Inthe implementation illustrated, the probe 104 is first rinsed (Block502) to avoid contamination of the sample. For example, as shown in FIG.1C, the autosampler 110 may cause the probe 104 to be moved to andinserted within the rinse station 112. The first valve 118 is actuatedto its first state so that the second port 124 of the first valve 118 isconnected with the third port 126 to couple the capillary 114 to line156. The second valve 120 is actuated to its second state so that thefirst port 134 of the second valve 120 is connected with the second port136 to couple line 156 with line 166. In this manner, a vacuum isapplied to capillary 114 to draw rinse fluid through the probe 104, thecapillary 114, first valve 118, line 156, second valve 120, and line166. The rinse fluid is then transported to the waste receptacle 176 viawaste line 170.

Gas may be injected through the probe 104 while the probe 104 is rinsed(Block 502). As shown in FIG. 1A, injection of gas by the sampleintroduction system 102 may be accomplished by actuating the first andsecond valves 118, 120 to their first state while the probe 104 isinserted within the rinse station 112 by the autosampler 110. The secondport 124 of the first valve 118 is thus connected with the third port126 to couple the capillary 114 to line 156, while the first port 134 ofthe second valve 120 is connected with the fourth port 140 to coupleline 156 with line 158 so that gas is supplied to the probe 104 from thegas source 160. The second valve 120 may be actuated to its first stateeither before or after injection of the gas to draw the rinse solutionthrough the probe 104 as described above.

Diluent may then be taken up into the probe 104 and/or the capillary 114(Block 504). The autosampler 110 may cause the probe 104 to be insertedinto a supply of diluent. The first valve 118 is actuated to its firststate so that the second port 124 of the first valve 118 is connectedwith the third port 126 to couple the capillary 114 to line 156. Thesecond valve 120 is actuated to its second state so that the first port134 of the second valve 120 is connected with the second port 136 tocouple line 156 with line 166. In this manner, a vacuum is applied tocapillary 114 to draw the diluent into the probe 104 and capillary 114.

Next, a segmentation bubble may be taken up by the probe 104 (Block506). For example, the autosampler 110 may cause the probe 104 to beremoved from the supply of diluent. The first valve 118 is againactuated to its second state, while the second valve 120 is actuated toits second state so that the vacuum is briefly applied to the capillary114 to draw atmospheric gas (e.g., air) into the probe 104 to form thesegmentation bubble.

The sample is then taken up by the probe 104 (Block 508). For example,the autosampler 110 may cause the probe 104 to be moved to and insertedwithin a container 106 that contains an undiluted sample. The firstvalve 118 is again actuated to its second state, while the second valve120 is actuated to its second state so that a vacuum is applied to thecapillary 114 to draw the sample into the probe 104. It is contemplatedthat the segmentation bubble may be taken up by the probe as theautosampler 110 moves the probe from the supply of diluent to thecontainer 106 that contains the sample to be taken up by the probe 104.

A second bubble may then be taken up by the probe 104 (Block 510) behindthe sample. For example, the autosampler 110 may cause the probe 104 tobe removed from the container containing the sample. The first valve 118is again actuated to its second state, while the second valve 120 isactuated to its second state so that a vacuum is briefly applied to thecapillary 114 to draw atmospheric gas (e.g., air) into the probe 104 toform the second bubble.

The sample and diluent are then expelled into a mixing container 106(Block 512). For example, the autosampler 110 may cause the probe 104 tobe moved to and inserted within an empty container 106. The first andsecond valves 118, 120 may then be actuated to their first state asshown in FIG. 1A. Thus, the second port 124 of the first valve 118 isconnected with the third port 126 to couple the capillary 114 to line156, while the first port 134 of the second valve 120 is connected withthe fourth port 140 to couple line 156 with line 158 so that gas issupplied to the capillary 114 from the gas source 160. The gas causesthe sample and diluent to be expelled from the capillary 114 and probe104 into the empty container 106. It is contemplated that the secondbubble may be taken up by the probe 104 as the autosampler 110 moves theprobe 104 from the container 106 that contains the sample to the mixingcontainer 106.

FIG. 6 depicts the probe 104 and capillary 114 of the sampleintroduction system 102 after taking up the diluent 602 and sample 604.Segmentation bubble 606 separates the diluent 602 and the sample 604,while second bubble 608 prevents leakage of the sample 604 from theprobe 104. In one or more embodiments, about 9 mL of diluent 602 andabout 1 mL of sample are taken up by the probe 104. However, it iscontemplated that amounts of diluent 602 and sample 604 may also betaken up by the probe 104.

Referring again to FIG. 5, an aliquot of the mixed sample and diluent isthen withdrawn from the mixing container 106 (Block 514). For example,as shown in FIG. 1B, after expulsion of the sample and diluent, thefirst valve 118 is again actuated to its second state so that the firstport 122 of the first valve 118 is connected with the second port 124and the third port 126 is connected with the fourth port 128 to couplethe sample loop 116 between the capillary 114 and line 156. The secondvalve 120 is also actuated to its second state so that the first port134 of the second valve 120 is connected with the second port 136 tocouple line 156 with line 166. In this manner, a vacuum is applied tothe probe 104 to draw the mixed sample and diluent through the probe 104and capillary 114 into the sample loop 116.

In some applications, expulsion of the sample and diluent from the probe104 (Block 512) may sufficiently mix the sample and diluent to allowwithdrawal of an aliquot of mixed sample and diluent. However, in otherapplications, additional mixing of the sample may be provided. In suchapplications, additional mixing may be provided via additional gasinjection, for example, in accordance with aspects of the procedure 200of FIG. 2.

In the discussion above, reference has been made to an exampleimplementation in which the sample introduction system 102 is used inthe analysis of oil samples. However, it is contemplated that the sampleintroduction system 102 is not limited to this implementation, butinstead may be used in the analysis of a variety of sample substances.For example, in other implementations, the sample introduction system102 may be used in the analysis of blood samples, wherein the diluentsupplied is water or another suitable liquid.

CONCLUSION

Although the invention has been described in language specific tostructural features and/or methodological acts, it is to be understoodthat the invention defined in the appended claims is not necessarilylimited to the specific features or acts described. Rather, the specificfeatures and acts are disclosed as example forms of implementing theclaimed invention.

What is claimed is:
 1. A method comprising: causing a probe to beinserted into a supply of diluent; causing diluent to be drawn from thesupply of diluent into the probe; causing the probe to be removed fromthe supply of diluent; causing atmospheric gas to be drawn into theprobe to form a segmentation bubble extending within the probe; causingthe probe to be inserted into a container containing a sample; causingthe sample to be drawn from the container containing the sample into theprobe, the segmentation bubble being configured to separate the diluentfrom the sample; causing the probe to be removed from the containercontaining the sample; causing the probe to be inserted into a mixingcontainer and the sample and the diluent to be subsequently expelledfrom the probe into the mixing container to mix the sample and thediluent; causing gas to be injected into the mixing container throughthe probe to further mix the sample and the diluent within the mixingcontainer; and causing an aliquot of the mixed sample and diluent to bewithdrawn from the mixing container through the probe.
 2. The method asrecited in claim 1, further comprising causing the probe to be insertedinto a rinse station containing rinse fluid prior to causing the probeto be inserted into the supply of diluent, and causing the rinse fluidto be drawn from the rinse station containing the rinse fluid throughthe probe.
 3. The method as recited in claim 2, further comprisingcausing a gas to be injected through the probe while the probe is rinsedat the rinse station.
 4. The method as recited in claim 1, whereincausing the atmospheric gas to be drawn into the probe to form asegmentation bubble comprises causing the atmospheric gas to be drawninto the probe while the probe is moved from the supply of diluent tothe container containing the sample.
 5. The method as recited in claim1, further comprising causing atmospheric gas to be drawn into the probeto form a second bubble extending within the probe prior to causing thesample and the diluent to be expelled from the probe into the mixingcontainer to mix the sample and the diluent, the second bubble beingconfigured to retard leakage of the sample from the probe.
 6. The methodas recited in claim 5, wherein causing the atmospheric gas to be drawninto the probe to form the second segmentation bubble comprises causingthe atmospheric gas to be drawn into the probe while the probe is movedfrom the container containing the sample to the mixing container.
 7. Asample introduction system comprising: a probe configured to be insertedinto a supply of diluent and subsequently into a container containing asample and subsequently into a mixing container; and a pump and a valveassembly together being operable to cause diluent to be drawn into theprobe, sample to be drawn into the probe, atmospheric gas to be drawninto the probe between the diluent and the sample, and the sample andthe diluent to be expelled from the probe into the mixing container tomix the sample and the diluent; wherein the pump is configured to applya vacuum to the probe and withdraw an aliquot of the mixed sample anddiluent from the mixing container.
 8. The sample introduction system asrecited in claim 7, wherein the sample introduction system furtherincludes an autosampler, the autosampler being configured to insert theprobe into a rinse station containing rinse fluid prior to inserting theprobe into the supply of diluent, and the pump being configured to applya vacuum to draw a rinse fluid from the rinse station through the probe.9. The sample introduction system as recited in claim 8, wherein thepump is configured to inject a gas through the probe while the probe isrinsed at the rinse station.
 10. The sample introduction system asrecited in claim 7, wherein the pump is configured to apply a vacuum todraw the atmospheric gas into the probe to form a segmentation bubbleextending within the probe while the probe is moved from the supply ofdiluent to the container containing the sample, the segmentation bubblebeing configured to separate the diluent from the sample.
 11. The sampleintroduction system as recited in claim 7, wherein the pump isconfigured to apply a vacuum to the probe to draw atmospheric gas intothe probe to form a segmentation bubble extending within the probe afterthe sample is drawn into the probe and prior to expelling the sample andthe diluent from the probe into the mixing container to mix the sampleand the diluent, the segmentation bubble being configured to separatethe diluent from the sample prior to expelling the sample and thediluents from the probe.
 12. The sample introduction system as recitedin claim 7, wherein the pump is configured to apply a vacuum to theprobe to draw atmospheric gas into the probe to form a segmentationbubble extending within the probe while the probe is moved from thecontainer containing the sample to the mixing container, thesegmentation bubble being configured to separate the diluent from thesample.
 13. A method comprising: inserting a probe into a supply ofdiluent; applying a vacuum to draw diluent from the supply of diluentinto the probe; removing the probe from the supply of diluent; applyinga vacuum to draw atmospheric gas into the probe to form a segmentationbubble extending within the probe; inserting the probe into a containercontaining a sample; applying a vacuum to the probe to draw the samplefrom the container containing the sample into the probe, thesegmentation bubble being configured to separate the diluent from thesample; removing the probe from the container containing the sample; andinserting the probe into a mixing container and expelling the sample andthe diluent from the probe into the mixing container to mix the sampleand the diluent; applying a vacuum to the probe and withdrawing analiquot of the mixed sample and diluent from the mixing container. 14.The method as recited in claim 13, further comprising inserting theprobe into a rinse station containing rinse fluid prior to inserting theprobe into the supply of diluent, and applying a vacuum to draw therinse fluid from the rinse station containing the rinse fluid throughthe probe.
 15. The method as recited in claim 14, further comprisinginjecting a gas through the probe while the probe is rinsed at the rinsestation.
 16. The method as recited in claim 13, wherein applying avacuum to draw atmospheric gas into the probe to form a segmentationbubble comprises applying the vacuum while the probe is moved from thesupply of diluent to the container containing the sample.
 17. The methodas recited in claim 13, further comprising applying a vacuum to theprobe to draw atmospheric gas into the probe to form a second bubbleextending within the probe prior to expelling the sample and the diluentfrom the probe into the mixing container to mix the sample and thediluents, the second bubble being configured to retard leakage of thesample from the probe.
 18. The method as recited in claim 17, whereinapplying a vacuum to the probe to draw atmospheric gas into the probe toform a second bubble extending within the probe comprises applying thevacuum while the probe is moved from the container containing the sampleto the mixing container, the second bubble being configured to retardleakage of the sample from the probe.
 19. A method comprising: insertinga probe into a supply of diluent; applying a vacuum to draw diluent fromthe supply of diluent into the probe; removing the probe from the supplyof diluent; applying a vacuum to draw atmospheric gas into the probe toform a segmentation bubble extending within the probe; inserting theprobe into a container containing a sample; applying a vacuum to theprobe to draw the sample from the container containing the sample intothe probe, the segmentation bubble being configured to separate thediluent from the sample; removing the probe from the containercontaining the sample; inserting the probe into a mixing container andexpelling the sample and the diluent from the probe into the mixingcontainer to mix the sample and the diluent; and applying a vacuum tothe probe while the probe is moved from the container containing thesample to the mixing container to draw atmospheric gas into the probe toform a second bubble extending within the probe, the second bubble beingconfigured to retard leakage of the sample from the probe.
 20. Themethod as recited in claim 19, further comprising inserting the probeinto a rinse station containing rinse fluid prior to inserting the probeinto the supply of diluent, and applying a vacuum to draw the rinsefluid from the rinse station containing the rinse fluid through theprobe.
 21. The method as recited in claim 20, further comprisinginjecting a gas through the probe while the probe is rinsed at the rinsestation.
 22. The method as recited in claim 19, wherein applying avacuum to draw atmospheric gas into the probe to form a segmentationbubble comprises applying the vacuum while the probe is moved from thesupply of diluent to the container containing the sample.
 23. The methodas recited in claim 19, further comprising applying a vacuum to theprobe and withdrawing an aliquot of the mixed sample and diluent fromthe mixing container.